Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
  • B01D53/1493—Selection of liquid materials for use as absorbents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
  • B01D53/1425—Regeneration of liquid absorbents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
  • B01D53/1456—Removing acid components
  • B01D53/1475—Removing carbon dioxide
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
  • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
  • C10L3/10—Working-up natural gas or synthetic natural gas
  • C10L3/101—Removal of contaminants
  • C10L3/102—Removal of contaminants of acid contaminants
  • C10L3/104—Carbon dioxide
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
  • F23J15/00—Arrangements of devices for treating smoke or fumes
  • F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
  • F23J15/04—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material using washing fluids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
  • B01D2252/20—Organic absorbents
  • B01D2252/204—Amines
  • B01D2252/2041—Diamines
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
  • B01D2252/20—Organic absorbents
  • B01D2252/204—Amines
  • B01D2252/20436—Cyclic amines
  • B01D2252/20442—Cyclic amines containing a piperidine-ring
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
  • B01D2252/20—Organic absorbents
  • B01D2252/204—Amines
  • B01D2252/20478—Alkanolamines
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
  • B01D2252/50—Combinations of absorbents
  • B01D2252/504—Mixtures of two or more absorbents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2256/00—Main component in the product gas stream after treatment
  • B01D2256/16—Hydrogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2256/00—Main component in the product gas stream after treatment
  • B01D2256/20—Carbon monoxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/30—Sulfur compounds
  • B01D2257/302—Sulfur oxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/30—Sulfur compounds
  • B01D2257/306—Organic sulfur compounds, e.g. mercaptans
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/30—Sulfur compounds
  • B01D2257/308—Carbonoxysulfide COS
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2258/00—Sources of waste gases
  • B01D2258/02—Other waste gases
  • B01D2258/0233—Other waste gases from cement factories
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2258/00—Sources of waste gases
  • B01D2258/02—Other waste gases
  • B01D2258/025—Other waste gases from metallurgy plants
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2258/00—Sources of waste gases
  • B01D2258/02—Other waste gases
  • B01D2258/0283—Flue gases
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2258/00—Sources of waste gases
  • B01D2258/05—Biogas
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
  • B01D53/1456—Removing acid components
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
  • Y02C20/00—Capture or disposal of greenhouse gases
  • Y02C20/40—Capture or disposal of greenhouse gases of CO2
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E20/00—Combustion technologies with mitigation potential
  • Y02E20/32—Direct CO2 mitigation

Definitions

• the invention relates to an absorption medium and a
• Alkanolamines used as absorption medium used as absorption medium.
• loaded absorption medium is regenerated by heating, releasing to a lower pressure or stripping, whereby the carbon dioxide is desorbed.
• the absorption medium can be reused.
• These methods are described, for example, in Rolker, J .; Arlt, W .; "Separation of carbon dioxide from flue gases by absorption” in Chemie Ingenieurtechnik 2006, 78, pages 416 to 424 and in Kohl, A.L .; Nielsen, R. B., "Gas Purification", 5th ed., Gulf Publishing,
• Desorption requires a relatively large amount of energy, and desorbs only part of the absorbed CO2, so that in one cycle of absorption and desorption, the capacity of the absorption medium is insufficient.
• US Pat. No. 7,419,646 describes a process for the deacidification of waste gases, in which an absorption medium is used which is two apart from one another during the absorption of the acidic gas forms separable phases.
• an absorption medium is used which is two apart from one another during the absorption of the acidic gas forms separable phases.
• a reactive compound for the absorption of an acidic gas in column 6 inter alia, 4-amino-2, 2, 6, 6-tetramethylpiperidine mentioned.
• the method of US Pat. No. 7,419,646 has the disadvantage that
• WO 2010/089257 describes an absorption medium for the absorption of CO2 from a gas mixture comprising water and a 4-amino-2,2,6,6-tetramethylpiperidine, wherein the amine may be alkylated at the 4-amino group.
• WO 2010/089257 describes the addition of solvents, such as sulfolane or ionic liquids, in order to keep the absorption medium in a single phase and to achieve a higher absorption capacity for CO 2.
• an absorption medium comprising a 4-amino-2, 2, 6, 6-tetramethylpiperidine having an n-alkyl substituent on the 4-amino group and a tertiary or a sterically hindered primary or secondary Contains alkanolamine.
• the invention therefore provides an absorption medium for absorbing an acidic gas from a gas mixture comprising water, an amine (A) of the formula (I)
• R is an n-alkyl group having 1 to 4 carbon atoms, and an alkanolamine (B) which is a tertiary amine or a sterically hindered primary or secondary amine.
• B alkanolamine
• the absorption medium according to the invention comprises water and an amine (A) of the formula (I), wherein R is an n-alkyl radical having 1 to 4 carbon atoms.
• R can therefore be a methyl radical, an ethyl radical, an n-propyl radical or an n-butyl radical.
• R is an n-propyl radical or an n-butyl radical, more preferably an n-butyl radical.
• Amines of the formula (I) can be prepared from commercial triacetonamine by reductive amination, ie by reacting triacetoneamine with an amine of the formula RH 2 and hydrogen in the presence of a hydrogenation catalyst.
• the absorption medium of the invention further comprises an alkanolamine (B) which is a tertiary amine or a sterically hindered primary or secondary amine.
• a sterically hindered primary amine in the sense of the invention is a primary amine in which the amino group is bonded to a tertiary carbon atom, i. to a carbon atom to which no hydrogen atom is attached.
• a hindered secondary amine in the sense of the invention is a secondary amine in which the amino group is bonded to a secondary or a tertiary carbon atom, i. to a carbon atom, to which only one or no
• Suitable alkanolamines (B) having a tertiary amino group are triethanolamine, N-methyldiethanolamine,
• Suitable alkanolamines (B) having a sterically hindered primary or secondary amino group are known from US 4,094,957 columns 10 to 16.
• Preferred alkanolamines (B) having a sterically hindered primary amino group are known from US 4,094,957 columns 10 to 16.
• the content of amines (A) of the formula (I) is preferably in the range of 5 to 50 wt .-% and the content of alkanolamines (B) is preferably in the range of 5 to 50 wt .-%.
• the content of amines (A) of the formula (I) in the range from 5 to 30% by weight and the content of alkanolamines (B) are particularly preferably
• Alkanolamines (B) in the absorption medium of the present invention is preferably in the range of 10 to 60 wt%, more preferably in the range of 10 to 45 wt%, and most preferably in the range of 10 to 30 wt%.
• the absorption media according to the invention have a high absorption capacity for CO 2 , which is generally higher than due to the absorption capacity of
• Absorption media containing only an amine (A) of the formula (I) or only an alkanolamine (B) is to be expected.
• the absorption media of the invention show sufficiently high absorption rates for a technical
• the absorption media according to the invention show no precipitation of a solid even without addition of a solvent in the absorption of CO 2 .
• the absorption medium according to the invention may contain, in addition to water, amines (A) of the formula (I) and alkanolamines (B), one or more physical solvents (C).
• the proportion of physical solvents (C) can be up to 50 wt .-%.
• Suitable physical solvents (C) are sulfolane, aliphatic
• Acid amides such as N-formylmorpholine, N-acetylmorpholine, N-alkylpyrrolidones, in particular N-methyl-2-pyrrolidone, or N-alkylpiperidones, and also diethylene glycol,
• Alkyl ethers in particular diethylene glycol monobutyl ether.
• the absorption medium according to the invention contains no physical solvent (C).
• the absorption medium according to the invention may additionally contain other additives, such as corrosion inhibitors,
• Alkanolamines are known as suitable corrosion inhibitors, in particular those described in US 4,714,597
• Corrosion inhibitors can be chosen significantly lower in an absorption medium according to the invention than in a conventional, ethanolamine-containing absorption medium, since the absorption media according to the invention are significantly less corrosive to metallic materials than the commonly used ethanolamine-containing absorption media.
• the wetting-requiring additive used is preferably the nonionic surfactants known from WO 2010/089257 page 11, line 18 to page 13, line 7, zwitterionic surfactants and cationic surfactants.
• Alkanolamines are known as suitable defoamers.
• the gas mixture is in contact with the absorption medium according to the invention
• the acidic gas for example CO2, COS, H 2 S, CH 3 SH may be or S O2.
• the gas mixture may also contain several of these acid gases side by side.
• the Gas mixture as acidic gas CO 2 and / or H 2 S, more preferably CO2.
• the gas mixture can be a natural gas, a methane-containing biogas from a fermentation, composting or
• Wastewater treatment plant a combustion exhaust gas, an exhaust gas from a calcination reaction, such as the burning of lime or the production of cement, a residual gas from a
• Blast furnace process for iron production or a resulting from a chemical reaction gas mixture such as a carbon monoxide and hydrogen
• the gas mixture is a synthesis gas, a natural gas or a combustion exhaust gas.
• the gas mixture preferably has a content of CO 2 in the range from 0.1 to 60% by volume, more preferably in the range from 1 to 40% by volume, before being brought into contact with the absorption medium.
• Any apparatus suitable for contacting a gaseous phase with a liquid phase may be used in the method of the present invention to contact the gas mixture with the absorption medium.
• membrane contactors for example, membrane contactors, radial flow scrubber, jet scrubber, venturi scrubber, rotary scrubber packed columns, packed columns or tray columns. Particular preference is given to absorption columns in the
• the absorption of the acidic gas is preferably carried out at a temperature of
• the Temperature of the absorption medium particularly preferably 30 to 60 ° C when entering the column and 35 to 70 ° C when exiting the column.
• the absorption of the acidic gas is preferably carried out at a pressure of the gas mixture in the range of 0.5 to 90 bar, more preferably 0.9 to 30 bar.
• the pressure of the gas mixture is preferably carried out at a pressure of the gas mixture in the range of 0.5 to 90 bar, more preferably 0.9 to 30 bar.
• An absorption of CO 2 from synthesis gas is preferably carried out at a pressure of the gas mixture in the range from 1 to 90 bar, more preferably 5 to 60 bar,
• An absorption of CO2 from natural gas is preferably carried out at a pressure of the gas mixture in the range from 5 to 90 bar, more preferably 10 to 80 bar,
• Combustion exhaust gas is preferably carried out at a pressure of the gas mixture in the range of 0.8 to 1.5 bar, particularly preferably 0.9 to 1.1 bar, so that the
• Combustion exhaust gas does not have to be compressed before.
• the acidic gas is CO2 and CO2 absorbed in the absorption medium is desorbed by raising the temperature and / or reducing the pressure, and the
• cyclic process of absorption and desorption CO2 can be completely or partially separated from the gas mixture and obtained separately from other components of the gas mixture.
• desorption may also be performed by stripping the CO2 laden absorption medium with a gas. If water is also removed from the absorption medium during the desorption of CO2, the
• Absorption medium may be added to water before reuse for absorption if necessary.
• For the desorption it is possible to use all apparatus known from the prior art for the desorption of a gas from a liquid. Desorption is preferably carried out in a desorption column.
• the desorption of CO2 can also be carried out in one or more flash evaporation stages.
• the desorption is preferably carried out at a temperature in the range of 30 to 180 ° C.
• the desorption of CO2 is preferably carried out at a temperature of the absorption medium in the range of 50 to 180 ° C, particularly preferably 80 to 150 ° C.
• the temperature during the desorption is preferably at least 20 ° C., more preferably
• the desorption of CO2 is preferably carried out at a total pressure in the gas phase in the range of 0.01 to 10 bar, in particular 0.1 to 5 bar.
• the pressure during the desorption is preferably at least 1.5 bar, particularly preferably at least 4 bar, below the absorption pressure and is most preferred
• the inventive method can be used in simply constructed systems, as used in the prior art for gas scrubbing with aqueous solutions of ethanolamine and achieved one improved compared to ethanolamine
• the desorption is carried out first by
• Flash evaporation stages the pressure is preferably lowered to 1 to 5 bar, more preferably to 1 to 2 bar.
• the stripping in the desorption column is preferably carried out at a temperature of the absorption medium in the range of 60 to 100 ° C.
• Absorption medium determined. The so determined
• Me-TAD 4-methylamino-2, 2, 6, 6-tetramethylpiperidine
• Pr-TAD 4- (n-propylamino) -2,2,6,6-tetramethylpiperidine
• Bu-TAD 4- (n-butylamino) -2,2,6,6-tetramethylpiperidine
• the temperature at which segregation of the CO2-laden and CO2-free absorption medium occurs on heating was also determined.
• the absorption medium was saturated with pure CO2 at 1 bar and 20 ° C. before closing the glass container.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Analytical Chemistry (AREA)
• Organic Chemistry (AREA)
• Mechanical Engineering (AREA)
• General Engineering & Computer Science (AREA)
• Gas Separation By Absorption (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Citations (9)

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• 2011
  • 2011-06-10 EP EP11169492A patent/EP2532412A1/de not_active Withdrawn
• 2012
  • 2012-05-25 EP EP12723504.2A patent/EP2717995B1/de not_active Not-in-force
  • 2012-05-25 EA EA201301357A patent/EA024132B1/ru not_active IP Right Cessation
  • 2012-05-25 AU AU2012266660A patent/AU2012266660B2/en not_active Ceased
  • 2012-05-25 ES ES12723504.2T patent/ES2550520T3/es active Active
  • 2012-05-25 MY MYPI2013004256A patent/MY161687A/en unknown
  • 2012-05-25 CN CN201280028524.0A patent/CN103635247B/zh not_active Expired - Fee Related
  • 2012-05-25 US US14/124,472 patent/US20140090558A1/en not_active Abandoned
  • 2012-05-25 CA CA2838932A patent/CA2838932C/en not_active Expired - Fee Related
  • 2012-05-25 PL PL12723504T patent/PL2717995T3/pl unknown
  • 2012-05-25 HU HUE12723504A patent/HUE025827T2/en unknown
  • 2012-05-25 WO PCT/EP2012/059824 patent/WO2012168095A1/de active Application Filing
• 2013
  • 2013-10-11 TN TNP2013000416A patent/TN2013000416A1/fr unknown
  • 2013-11-29 MA MA36510A patent/MA35161B1/fr unknown
  • 2013-12-09 ZA ZA2013/09256A patent/ZA201309256B/en unknown

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